AU498552B2 - Hydrotreatment catalyst - Google Patents

Description

(CONVENgTION. onc- o Form 4A

A PATEN

00

Ix 78034/75 o 0 r __COMPfiGN'IE FRANCAISE DE RAFPTNAGF. 3 We of' 5 rue Michel Ange, 75116 Paa-is, lurL no. Tle France 'CPj)AL ALLkOW~2 nrrumber hereby apply for the grant of a Patent for an invention entitled:" 0 iiw of cb *0 uappikaou(Cu) CjJ.TALYSTS 11?Olt TTL HYDrTPATMM5T OF~ HTDCJROXUONS A

MOCESS FO'01 PEArAIO1N .A11,D AILC7'O~JF IAD ATALYSTS.

which is described in the accompanying complete specification. This application is a

Convention aplication and is based (on the application numbered

itjO iOOrt 74 OL4 395 NaumeouI basIr CunItry ir Cott"trio~s.a ~fd for a patent or similar protection madec in France bast, date or date% 13th FVebruary, 1)74.

-Maddress foi service is Messrs. Edwd. Waters Sons, Patent Attorneys, Our 50 Quieen =kxft6treet, Melfiourne, Victoria, Australia.

DATED this 7th day of F ebrua.-y 19

SIC %a COMFAGNTE 1, I2ASE DR 1RAFFINJAGE ture 0f or 6s0;1of company and 8ignatmres of ita Officers aa preacribed by its Aruiclesofc by AssOociationl.

470MMONWEALcH OF AUSTRALI.A Patents Act 1952,1962 DECLARATION IN SUPPORT OF A CONVE7TMhN APPLICATION FOR A PATENT OR PATENT OF ADDITION

In support of the CoG enion 8 0 M175ixpcation md Company. ~te.,COMPA.GNIE FR.AN.CAISE DE-RAFF.IN.AGE..,-,-- AociqtyAnonym

(hereinafter referred to as the apphrant, for a Patent lie c $,ottitle for an invention entitled:( QATATU!--$. W.QP T I_ YFO.I.TMiD, XI. _Q..'jYW~Q4~L 2 ~1QP JP~LE~i.TI~.'l 3Y~QOFQ~.. ILC2LY t

J3) Jean F E B V A Y inw~art Lta0i Naoir

a ndA did res o ec i b .N .i autorni7,d to nuakc do solemnly and sincerely declare as follows: 1. 1 am authorised by the applicant for the patent. *to make this declaration en its behalf.

lre2. The basic app)lication as dcfined by Sction 141 of the Act was laso bai made iu"' FRK

CoIunWrnby onte J~h dyo.Fbtay .9 by..S.ci6.t Anoniymie datz, or dtvstt anti basic dt NA~ D AFIIG 'a Applicinttor.. ie 1MPA GNI FAqQA1ZDZRF1NkE 'a Applicants.

,,Hue Joseph Edoua rd WEISANG r S ia -76

and Addrm~ of &l tl LE FAVRE (RN I nvento it IZatiors. and Philippe ENGELHARDP 1.97? me-T.. Faure LE IAVRE... (FRANCU). xia6re the actual Inver tor sof the invention and the facts upon which tlie applicant is entitled to make the application are as follow: The applicant is the assignee of tlie.. aaid actual J m ezators.

4. The basic application referred to in paragraph 2 of this Declaration 0 was the first application made in a Convention coirntry in respect of the invwention the subject of the applicati M

DECLARED at. xne IQiA.

())sixoturc. .da (t )o

To: Tiim COMAMISSIONFR OF Edwd. Waters Soiu, PAR-

(11) AU-B 78034/75

(12) PATENT SPECIFICATION ABRIDGEMENT (19) AU (21) 78034/75 498552 (22) 10.2.75 (23) 10.2.75 (24) 13.2.74 (31) 74 04 895 (32) 13.2.74 (33) FR (43) 12.8.76 (44) 15.3.79 (51) B01J 11/08 C10G 13/10 (54) HYDROTREATMENT CATALYST (71) COMPAGNIE FRANCAISE DE RAFFINAGE (72) WEISANG, J.E. ENGELHARD, P. (74) WM (56) 83180/75 07.93 20.6 09.37 7738/55 210321 07.9 20.6 (57) CLAIM 1. A catalyst for the hydrotreatment of hydrocarbons comprising a porous refractory mineral oxide carrier incorporating a halogen element, present in combined form, said catalyst being characterized by the fact that it comprises in combination the following metals, in the free state or combined: from 0.02 to based on the total weight of the catalyst, of at least one platinum-group metal; from 0.02 to based on the total catalyst weight, of at least one additional metal from the group consisting of molybdenum, chromium and manganese; from 0.02 to based on the total catalyst weight, of tin; and optionally from 0.05 to 0.5% of sulfur, based on the total catalyst weigh,..

ND 9,2

Form COMMONWEALTH OF AUS'".-RALIA

PATENTS ACT 1952-69

COMPLETE SPECIFICATION (ORIGINAL)

78034/75 Class Int. Cla s Application Number: Lodged:

S 0 S 0e*.

0S S

S Complete Specification Lodged: w S5* Acceptedi adc 4L

5 S. 55 Published:, ri 4 *5 *0 S S S Priority: .0^ 1 59 Vw^ S

Related Art: 0

B S

S 555

Name of Applicant: COMPAGNIE FRANCAISE DE RAFFINAGE.

S* S 6 o Address of Applicant 5, rue Michel Ange, 75116 PARIS, France.

0. Actual Inventor: JOSEPH-EDOUARJ) WEISANG and PHILIPPE ENGELHARD.

Address for Service EDWD. WATERS SONS, 0 O50 BE HUSSflL STREET, MELBOURNE, AUSTRALIA. 3000.

Complete Specification for the invention entitled:

"CATALYSTS FOR THE HYDROTREATMENT OF HYDROCARBONS AND A PROCESS FOR PREPARATION AND APPLICATION OF SAID CATALYSTS'

The following statement is a full description of this invention, including the best method of performing it known to US.

SThe present invention relates to catalysts for the

hydrotreatment of hydrocarbons, and more particularly of

petroleum fractions whose distillation range corresponds to

that of gasoline and of naphtha. It also comprises a process

for preparation of said catalysts.

In this specification and in the claims, "catalytic

hydrotreating or hydroconversion processes" means processes

applied to hydrocarbon charge stocks in the presence of hydrogen

which entail isomerization, cyclization, dehydrocyclizatior and/

IC or aromatization reactions. These reactions may be carried out CO C separately or, as is the case with hydroreforming, simultane- 0° t) *a ously, which is particularly advantageous, as will be seen

further on, with the catalysts in accordance with the invention. S

In the case of hydroreforming, one of the reactions hydro- S.

S" cyclization or hydroisomerization, for example may prepon-

derate, depending on the reaction conditions, the nature of the

charge, and the nature of the catalyst.

It is a well-known fact that there is at present a

great upsurge in catalytic hydrotreating processes for hydro-

.20 carbons. It i6 linked, on the one hand, to the need of the o 5

refineries for a source of gasoline of very high octane rating

which is used either as is or, more generally, after being

blcnzed with a petroleum fraction having a nearby boiling

range but a lower octane rating, and, on the other hand, the

need of the petro-chemical industry for a source of aromatic

hydrocarbons, as these are the important raw materials of the

plastics industry. The metals of group VIII of the periodic

table, and particularly platinum, deposited on an acidic or

w-akly acidic refractory mineral carrier, are widely used as

hydrotreating catalysts.

It is known that for the purpose of increasing the

octane rating of the effluent obtained as well as the liquid

yield, and particularly the yic3d in aromatic hydrocarbons,

without having to appreciably raise the platinum content,

bimetallic and trimetallic catalysts have come into use, among

which might be mentioned, for example:

Pt-Sn, Pt-Pb, Pt-Ge, Pt-Re, Pt-lr, Pt-Au, Pt-Cu,

Pt-Sn-Re, Pt-Sn-Ir, Pt-Sn-Ge, Pt-Pb-Re, Pt-Ge-Re and Pt-Re-Ir.

M By adding different metals, very interesting hydro- C) cO treating catalysts can be obtained.

Thus an object of the present invention is to produce catalysts for the hydrotreatment of hydrocarbons which result *e e o in a better octane rating for the effluent and give a higher

liquid yield than is obtained when a catalyst is used which

consiscs only of platinum or one or more platinum-group metals

sup ported on a refractory mineral oxide carrier.

In +his specification, "platinum-group metal" means

one of the following metals: ruthenium, rhodium, palladium, osmium, iridium, and platinum. .20 /A-e ofrrod ombodimffnt of the present inventionie-- a

catalyst for the hydrotreatmert of hydrocarbons comprising a

refractory mineral oxide carrier and a halogen element present

in combined form, said catalysts comprising in combination the

following metals, in the free state or co.bined:

From 0.02 to and preferably from 0.10 to

0.70%, on the basis of the total weight of the catalyst, of at

least one metal from the platinum group;

From 0.02 to and preferably from 0.02 to

0.60%, based on the total catalyst weight, of at least one

metal from the group consisting of molybdenum, chromium and manganese; From 0.02 to and preferably from 0.05 to

1.00%, based on the total weight, of tin; and possibly from 0.05 to 0.5% of sulfur, based on

the total catalyst weight.

The invention relates more particularly to catalysts

as defined above and in which

S(1) Said carrier has a specific surface greater than 2 o I rt-&J6) 3. m per gram~and a specif c pore volume greater than 0.1 cm3

per gram, and 0 The halogen content is comprised t tween 0.4 and De Do C 2% and prefei:ably between 0.5 aid based on the total C 4 catalyst weight. ee BC A further preferred embodiment of the present

invention is a process for preparation of the hydrotreating

catalysts defined above, said process being/I the type

involving at least one impregnation of the porous carriers witi

at least one solution containing at least one of the elements

to be deposited. At least one of the impregnating solutions

C CCB .20 for said process comprises either cations formed from molyb- GO: C3

denum and/or chromium and/or manganese elements, or anions

containing molybdenum and/or chromium and/or manganese elements.

Another embodiment of the present invention is an

improvement to the process of preparation described above,

5o said improvement comprising subjecting the catalysts to a

reduction and possibly a sulfurizatiun before they are used.

Lastly, still another embodiment of the invention is

the application of the catalysts defined above to the

reforming of a hydrocarbon charge.

The carriers of the catalysts in accordance ,-th the invention are the refractory materials customarily employed with hydrotreating catalysts. They have adequate specific surface and specific pore volume, the specific surface prefer- ably comprising between 15 and 350 m 2 pergram, preferably between 100 and 350 m per gram4 and the specific pore volume being greater than 0.1 cm 3 per gram. These materials moreover, may be acidic or weakly acidic (acid sites), either in the sense of Bronsted or in the sense of Lewis. The measure of the acidity of the carrier characterizes the pres- ence and magnitude of these sites. (Hugues, White, Journal of o Catalysis, 1969, vol. 13, pages 58-64; Tanaka and Ogasaware,

Journal of Catalysis, 1970, vol. 16, pages 157-163). Alumina

and the aluminosilicates, for example, are well suited. The catalysts may be prepared by techniques for

impregnation of a carrier by means of a solution containing the

elements to be deposited. The various metals may be deposited

in any desired order. However, the applicant has found that

the platinum is advantageous deposited after the -In. Thus it

will be preferable:

either to deposit the tin and tien at least one

1 metal from the group consisting of chromium, manganese and

molybdenum, and lastly at least one of the platinum-group

metals, in which case the two last-mentioned depositions may

be made simultaneously, if desired,

or to deposit at least one metal from the group

consisting of chromium, manganese and molybdenum, and then the

tin, and after that at least one of the platinum-groupometals,

in which case the two first-mentioned depositions may be made

simultaneously, if desired. However, it will be preferable to

first deposit the tin.

After each deposition of a metal other than one of

the platinum-group metals, the solid obtained may be calcined 0 at a temperature comprised between 400 and 700 C, and prefer-

ably between 500 and 6C0°C. Following the deposition of at

least one of the platinum-group metals, the catalyst obtained

AScalcined, preferably at a temperature below 530°C. The most advantageods catalysts are those whose

contents in platinum-group metals, tin, and metals from the

o- group consisting of molybdenum, chromium and manganese are *9o:

O*'Q C comprised between 0.02 and and preferably between 0.10 and so00 0.70%; between 0.02 and and preferably between 0.05 and 1%;

o and between 0.02 and and preferably between 0.02 and 3.60%,

respectively, these percentages being based on the total weight 00.

of the catalyst.

The platinum-group metal content is that which is

usually employed in multimetallic catalysts for the hydrotreat-

ment of hydrocarbons. To secure satisfactory catalystic

properties, the content in this type of netal is preferably

greater t]an however, for catalyst-cost reasons, said

-20 content usually is limited to 0.70%.

Similarly, the metal content of the group consisting

of molybdenum, chromium and manganese is between 0.02 and 2%.

Below 0.02%, the improvement in the properties of the usual

catalyst containiLag on ly a metal such as platinum supported

on a porous carrier is not appreciable; nor is it worthwhile

above It has alsc been found that the most efficacious

contents are those comprised between 0.02 and 0.60%, as no

improvement in catalytic properties is observed above 0.60%.

The same applied to the tin. The content in this

metal may range from 0.02 to however, a content comprised between 0.05 and 1% is the most advantageous.

The halogen content of the catalyst is well known in

the art. It may range from 0.4 to but the best results

are obtained with halogen contents between 0.5 and 1.6%,

chlorine being the preferred halogen.

The acidity of the carrier may be altered prior to

deposition of the eleLients, or between the depositions when

they are not s-multELnecus. In particular, the carrier on

,060 which the molybdenum and/or the manganese and/or the chromium 06 0 ,_nd the tin have been deposited may bc subjected to a treatment S* 0 0 00 with an acid hydrochloric acid, for ex.mple before or 00 6>_ 000 during the deposition of a platinum-group metal. In the case 0*

.oo of manganese, however, it is preferable to effect the acid 66 00* 6 6 l 9 v treatment only just before tho manganese is deposited. Said

acid treatment will be describeO fuither on in conjunction with 6@ 0* 0 the examples.

It has be:n found that in the impregnating solution 1 0* a* 0

containing the elements of molybdenum and/or manganese and/or

chromium, and in that containing tin, these elements may be

present in different states. Thus, they may be present as

cations at a degree of oxidation which is stable under the

operating conditions and in the working medium, for example,

Cr or Mn They may also enter into the formation of

anions, such as CrO, 2 or MnO-4, for example.

The tin may be deposited by means of stannous

chloride or stannic chloride solutions, for example.

The halogen present in the catalyst in accrdance

with the invention will generally be chlorine in combined form.

It has been further found that the stability with

*0 time of the catalytic properties may be considerably improved by having the catalyst undergo a treatment before it is used.

Such treatment consists in carrying out a reduction at about

500 0 C, as is done with most catalysts for the hydrotreatment

of hydrocarbons, and a sulfurization of the catalysts, which may 0 be effected at a temperature ranging from 350 to 400 C with

sulfurized hydrogen diluted in hydrogen, with low-molecular-

weight mercaptans, or with organic sulfurs, for example. This

Streatment is most worthwhile on the industrial scale as it has

the effect of prolonging the service life of the catalyst with-

0 out its having to be regenerated by the means known in tie art. *00 The catalysts so treated may contain from 0.05 to 0.5% of

sulfur, based on the elemental state, in relation to the total catalyst weight.

The present invention is illustrated by the examples

which follow and which are not intended to be limitative.

•Most of these examples relate to hydroreforming of normal

heptane. However, this particular charge stock does not

constitute a limitation of the field of application of the

catalysts in accordance with the invention, which may be used

successfully, for example, in hydroreforming a hydrocarbon

charge whose boiling temperature is comprised between 35 and

2500 C and whose sulfur content is under 10 ppm and, if possible,

under I ppm, as will be seen in the second part of Example III. EXAMPLE I

An alumina is used in the form of extrusions whose

characteristics are as follows:

Average diameter of extrusions 1.5 mm

Specific surfaces 190 m 2 /g

Pore volume 0.51 cm3/g

i 30 Average pore radius 53

W".S I -I .fIe IaaiB!

Chlorine content

(measured by x-ray fluorescence) by weight of alumina

This alumina is calcined for four hours at 600 0 C and

will be used as a carrier for the catalysts prepared and tested

in this example. This example involves the preparation of a

control catalyst T and of the three catalysts I, II, and III.

PREPARATION OF CONTROL CATALYST T

100 g of the above alumina is immersed in 250 cc of

.9. :io an 0.1 N solution of hydrochloric acid. After dewatering at 9 0 orainary temperature, the alumina is contacted with a circul- t00 9 9 9 ating solution of hexachloroplatinic acid whose initial 99 9 0 6 9 platinum concentration is such that the catalyst contains from 9 9. 9 «o 0.355 to 0.40% by weight of platinum.

After dewatering followed by drying at 100°C, the *0

99 e solid is calcined at 5350°C in a muffle kiln. The catalyst so 9

9 obtained contains 0.355% by weight of platinum. .99 a

PREPARATION OF CATALYST I 9

100 grams of alumina carrier on which 0.20% by weight

9 56 of tin has first been deposited is immersed in 125 cc of a 9

solution containing 10 cc of hydrochloric acid R.P. To this,

125 cc of a solution which likewise contains 10 cc of hydro-

chloric acid R.P. as well as 0.3568 g of ammonium paramolybdate

is added to give the desired molybdenum content in th, final

catalyst. The alumina granules are dewatered, dried, pre-

calcined for two hours at about 350°C, then calcined at 600°C

for two hours in a muffle kiln. The calcining temperature

should preferably be above 500°C. The solid obtained is then

treated with 250 cc of an 0.1 N solution of hydrochloric acid,

1fe 50 then contacted with a solution of hexachloroplatinic a^id

-9-

~~adfl~r 2A.4~ whose initial platinum concentration is such that the final catalyst always contains from 0.35 to 0.40% by weight of 0 platinum. After dewatering followed by drying at 120 C, the 0 solid is calcined for two hours at 530 C in a muffle kiln.

In this way, catalyst I is obtained. Its compos-

ition is given in Table I. PREPARATION OF CATALYST II

The tin and the chromium are deposited simultaneously

on the alumina carrier. To this end, 100 g of alumina carrier 2

is immersed in a solution containing 0.461 g of chromium 3 chloride CrCl.6H2 0 and 0.380 g of stannous chloride SnCl 2 .H2 0,

dissolved in 115 cc of water and 10 cc of hydrochloric acid R.P. The rest of the preparation procedure (drying and e.

calcining steps and deposition of the platinum) is identical

in every respect with that of catalyst I. REPARATION OF CATALYST III

"100 g of alumina carrier which already contains the tin (d-posited by impregnation) is immersed in an 0.1 N hydro-

oo chloric acid solution containing 0.912 g of manganese nitrate a

and such an amount of hexachloroplatinic acid that the final

catalyst obtained contains from 0.35 to 0.40% by weight of

platinum.

The solid obtained is dewatered, dried at 1200C, and

then calcined at 530 0 C. Catalyst III contains tin, manganese

and platinum. Its composition is given in Table I.

9* *9C* 0960 be Ce 9. 6 0 99 6 99 99 9 6 6 9 966 96 9 0 9 0 9 0 9 0 9 9 0~ 0 eceSo 9 09 00 6 Thbl~i 6 60 6~ 46 9

78034175 Composition of Catalysts T, I, II and III

1.20

.21

'.21 a a. t. CtI a a a a..

aa a T~bl~ *I

7803 4/75 Composition of Catalysts T, I, TI arid III

Designation of catalysts J PtS~ C1% Mn% Cr'% No% n

T 0.35 1.45

1 0.39 1.21 0.24 0.20

11 0.39 1.13 0.07 0.21

II0.38 1.40 0.15 0.21

.1 _I

Catalytic tests are then run as described below: A

gas stream of hydrogen and normal heptane is passed, at a

temperature of about 520°C and under atmospheric pressure, over

2 m 3 of catalyst placed in a small reactor. The sulfur

content of the n-heptane is under I ppm. The hourly space

velocity of the gas mixture, usually expressed as v/v/hr liquid

(volume velocity per hour, measured in the liquid state, volume

U, of charge passing per hour per unit of volume of catalyst), is fi a C 0.5. The hydrogen/heptane ratio in the gas stream is 18:1.

910 00 The reactor effluent is analyzed by chromatography in the gaseous phase. *1 *4 The results obtained with ccatalysts T, I, II and III Ce

w a. are shown in Table II.

a *4 C p 0

9*

CC S 4.

4

6L_/* -12-

9 Ee 0 0

0 C be be*. 09.0 C 0 S 00e0 *TIMLE TIr

7830 34/75

Catalyst Characteristic values of effluent Operating -time (Wt. of charge) (hours) 1 3

T C1 to C4 42.4 40.3 39.2 i" to ic7 1.3 4.1 Aromnatics 56.3 55.3 52.1

C1 to C4 16.3 16.55 16.00

to ic7 5.7 4.45 4.00 Aromnatics 80.0 79.0 80.0 4,

ii C1 to C4 17.1 9.9 iC 5 to ic7 2.0 2.7 Aromatics 80.9 87.4 88.2 4

III C1 to C4 10.0 6.5 to ic7 2.5 2.5

Aromnatics 87.5 91.0 90.0 a 00 0 4 0 so 'Q 0 0 0

0 0 0 0 0 0 0 0 00*0 f Tfl I

'1803 4/75 I

Operating ti.ine Catalyst Characteristic values of' effluent (Wt. of' charge) (hours) 1 35

C1 to C4 42.4 40.35 39.2 to ic 1.15 4.1 Aroma-ti- cs 56.35 55.35 52.1

C1 to C4 16.15 16.555 16.00 to iC' 15.7 4.45 4.00 5 7 Aromaticsa 80.0 79.0 80.0

IIC 1 to C4 17.1 9.9 9.15 to IC7 2.0 2.7 Aromatics 80.9 87.4 88.2

IIC 1 to C4 10.0 6.5 to IC7 2.5 2.5

Aromatics 87.5 91.0 90.0

The table shows, for each catalyst and after 1, 3 and

hours of operation, the values of the composition of the effluent in hydrocarbons

having four or less carbon atoms, this value being represent-

ative of the cracking of the charge;

the fraction iC to iC in the effluent (light

liquids); and the composition of the effluent in aromatic hydro-

carbons, which is representative of the activity of the

catalysts for the reforming of hydrocarbons.

C? It is apparent that the three catalysts I, II and III 00 are good reforming catalysts. It is further seen that, under

the conditions selected, catalyst I has slightly greater

cracking activity than catalysts II and III.

EXAMPLE II

In this example, catalytic tests are run under

hydrogen pressure and the following conditions:

25 cm of catalyst is placed in a stainless-steel

reactor and a stream of pure and dry hydrogen is passed over

the catalyst for two hours, the temperature of the latter being o 0

Smaintained at about 500OC and the pressure in the reactor being

maintained at 7 bars. The charge consisting of normal heptane

is then introduced with an hourly space velocity of 2 and a

ratio of moles of hydrogen introduced to moles of normal

heptane introduced of

Samples taken from the reactor effluent permit

determination, on the one hand, of the liquid yield, by simple

weighing, and, on the other hand, of the equivalent octane

number of the liquid, by applying to chromatographic analyses

of said liquid the ASTM blend numbers appearing in the graphs with which those skilled in the art are familiar. The tests are performed at a fixed octane number, that is to say, as soon as a decrease in octane number is observed, the reactor temperature is raised in order to bring the octane number again to the level originally selected. The variation ;f the reactor temperature as a function of time closely resembles a straight line whose slope is measured. The milder the slope of the straight line, the better the catalyst, as the temperature then need to be adjusted M only very slightly in the course of time to secure the desired o octane number. By the same token, the limiting temperature of too*: use 139 reached more slowly and -the duiration of the service cycle is lengthened, which is a decided advantage in industrial 0* applications Table III shows the results of the tests so performed with catalysts T, I, II and III for -three octane numbers selected at the outset.

WPe

*8SC 55 aS aSaS at S. S 8 aa S# a 55 St 0 a 5 .5 S .6 5 S S S a 6000S a a 0. a *a.0S S o 0 5 @5 55 5 S a 58 55 05 0

TABLE III 78034/715

Designation Octane number initial tempoerature Temperature gradient vrgyil caaysieeceld )asafncCo of time

T 98 495 0.3353 55.7 103 499 0.3435 61.0 108 507 0.310 55.8

1 98 502 0.105 60.2 I 103550 0.100 58.5 108 511 0.291 54.8

Ii 98 497 0.074 60.15 105 510 0.056 60.9 108 510 0.086 58.5

II98 502 0.070 59.9 103 509 0.082 60.2 108 515 3.132 60.0 cc 9 0 S c :00 00. c c c S 9 p

TABLE III 78034/75

Designation Octane number Initial temperature Temperature gradientAvrgyil of' catalyst selected (a C) as a function of time

T 98 495 0.3331 55.7 1035 499 0.3543 61.0 108 507 0.310 55.8

I 98 502 0.105 60.2 1015 509 0.100 58.5 108 511 0.291 54.8

II98 497 0.074 60.15 1015 510 0.056 60.9 108 510 0.086 58.5

III 98 502 0.070 59.9 1015 509 0.082 60.2 108 515 0.1152 60.0

The results reported in this table show that tha

catalysts in accordance with the invention are very good

reforming catalysts. In particular, the liquid yield is high

and the slope of the straight line representing the temperature

as a function of time is very mild by comparison with a

conventional platinum catalyst.

EXAMPLE III

The purpose of this exampla is to show the effect of

a sulfurization on the performance of the catalyst in accord-

9~S .10 a ance with the invention. To this end, catalysts containing pa..

a a. a the metals platinum, tin, molybdenum or manganese or chromium a

are sulfurized before being used in the hydrotreatment of a al

a. a a hydrogen charge. A gas stream of sulfurized hydrogen and

hydrogen in the volume ratio of 1/3 and 2/3, respectively, is

o S a• then passed over these solids at an average rate of about 5 to a S 6 liters per hour for four hours and at a temperature of about

a. 370°C. SOa The analysis of the catalyst is given in Table IV,

the percentages being weight per cent. TABLE !V

Catalyst Pt Cl% Mn% Cr% Mo% Sn% S%

IV 0.35 1.41 0.24 0.20 0.18

V 0.35 1.30 0.15 0.2" 0.08

VI 0.35 1.25 0.08 0.20 0.07

With catalysts IV, V and VI,/-at test

identical in all respects with one of Example I is then

performed and the characteristic values of the effluent are

I measured at the end of 1, 3, and 5 hours of operation. The

results of the various analyses are given in Table V. TABLE V

Catalyst Characteristic values of effluent Operating time (Wt. (hours) 1 3

IV C1 to C4 19.2 16.8 16.9

iC5 to iC7 4.1 4.5 5.3

"..oO Aromatics 76.7 78.7 77.8

V C1 to C4 7.4 5.8 4.7 0Q@

iC5 to iC7 1.7 1.5 1.2 8 0o Aromatics 90.7 92.7 94.1 000

*o S VI C1 to C4 6.9 4.0 8

to iC7 1.3 0.8 0.9

Aromatics 91.8 95.2 94.6

It is apparent that the performance of these three

catalysts is very good.

Moreover, a pressure test was run with catalyst IV

under conditions identical in every respect with those of

Example II, except for 0 the temperature, which here is only 480 C, and

the charge, which is a charge of hyarocarbons 0 whose initial point (distillation) is 76 C and whose end point

is 151 0 C, the PNA composition of the charge, expressed in

weight per cent, being as follows:

-18-

I

Paralffins '67.0% Naphthenes 23.0% Aromatics 10.0% Sulfur 0.,5 PPM Density of charge 0.727

The liquid effluent was analyzed and the equivalent octane number calculated (from graphs with which those skilled in the art are familiar). Table VI shows he-et 1-cei't-e-f the equivalent octane number as a function of test duration as 10 Go well as the evolution of the liquid yield. S.-

S.S TABLE VI r S 5 54 d

o o .5 Time of S S. measurement 19 1/2 h 31 1/2 h 43 1/2 h 55 1/2 h 67 1/2 h 79 1/2 h *0 S S.

Equivalent octane 118.3 116.8 117.2 112.3 116.45 118.9 number .c

'S S Liquid 63.7 65.7 66.4 69.0 69.2 65.0 S. p~. yield

so S S SI S It is apparent from this table that the performance 0

of catalyst IV is very good, particularly in view of the fact that the temperature of the conversion was maintained through- or.

out the -test at 4800 C, which is a rather low temperature for hydrore forming reactions.

Claims (1)

1. l~t~Ci~;w

   THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS:-

   1. A catalyst for the hydrotreatment of hydrocarbons

   comprising a porous refractory mineral oxide carrier incorpor-

   ating a halogen element, present in combined form, said

   catalyst being characterized by the fact that it comprises

   in combination the following metals, in the free state or

   combined:

   from 0.02 to based on the total weight of the

   S.0 catalyst, of at least one platinum-group metal;

   S O from 0.02 to based on the total catalyst weight,

   of at least one additional metal from the group consisting of a

   molybdenum, chromium and manganese; 0

   from 0.02 to based on the total catalyst weight,

   of tin; and optionally from 0.05 to 0.5% of sulfur, based

   on the total catalyst weight.

   S2. A catalyst according to Claim 1 wherein the content

   of said platinum-group metal is from 0.1 to of each of

   said molybdenum, chromium, or manganese is from 0.02 to 0.6%,

   tin is from 0.05 to 1.07, optionally from 0.05 to of

   sulfur based on the total catalyst weight..

   3. A catalyst as defined in Claim 1 or 2, characterized

   by the fact that said carrier has a specific surface greater

   than 15 mL per gram as determined by the B.E.T. method and a 3 specific pore volume greater than 0.1cm said catalyst

   having halogen content between 0.4 and based on the total

   catalyst weight.

   4. A catalyst according to Claim 3 characterized by the

   fart that its halogen content is between 0.5 and 1.6% based

   !7,n AI 7-

   mmm *u~i~~,~upi;i~irt~L~Vd ~U ~w~h~'Lg~bQ~df on the total catalyst weight.

   A catalyst as defined in any one of Claims 1 to 4,

   characterized by the fact that the platinum-group metal is

   platinum.

   6. A catalyst as defined in any one of Claims 1 to

   characterized by thL fact that the halogen incorporated in the

   .H catalyst is chlorine.

   7. A catalyst as defined in any one of Claims 1 to 6, 0 characterized by the fact that the carrier is an alumina whose 2 specific surface is comprised between 100 and 350 m /gram

   (determined by the B.E.T. method).

   8. A catalyst as defined in any one of Claims 1 to 7

   wherein said additional metal is only molybdenum.

   9. A catalyst as defined in any one of Claims 1 to 7

   wherein said additional metal is only chromium.

   10. A catalyst as defined in any one of Claim 1 to 7

   wherein said additional metal is only manganese.

   11. A catalyst as defined in any one of Claims 1 to 7

   wherein said additional metal is chromium or manganese.

   12. A catalyst as defined ir any one of Claims 1 to 7

   wherein said additional metal is a plurality of metals including

   molybdenum.

   13. A process for preparation of a catalyst as defined in

   any one of Claims 1 to 12, said process involving at least one

   impregnation of the porous carrier with at least one solution

   1AJ- 21 containing at least one of the elements manganese, molybdenum aud chromium, a platinum-group metal, and tin, at least one of the impregnating solutions comprising either cations formed from the elements manganese, molybdenum or chromium, or anions containing -he elements manganese, molybdenum or chromium and introduction of a halogen in single or combined form.

   14. A process as defined in Claim 13, further characterized

   by the fact that the deposition of tfhe tin is effected before

   OD the deposition of at least one of the platinum-group metals.

   o. 15. A process as defined in any one of Claims 13 and 14,

   characterized by the fact that before or during the deposition

   of at least one of the platinum-group metals the carrier is

   treated with a hydrochloric acid solution.

   16. A pro'css as defined in any one of Claims 14 and

   further comprising, after deposition of the metals other than

   the platinum-group metals, a calcination at a temperature

   comprised between 400 and 700 0 C, then, following the deposition

   of at least one of the platinum-group metals, a calcination at

   a temperature under 530°C, a reduction with hydrogen at a

   temperature of about 500°C, and optionally a sulfurization of

   "the catalyst with sulfurized hydrogen, low-molecular-weight mercaptans, or organic sulfurs.

   A process as defined in Claim 16 wherein said first

   calcination is between 500 and 600 0 C.

   18. A process for the hydroreforming of a hydrocarbon

   charge consisting in contacting the hydrocarbon charge, hydrogen

   and a catalyst as defined in any one of Claims 1 to 12 under hydroreforming conditions.

   19. A process for hydroreforming a hydrocaibon charge as defined in Claim 18 which cmprises the following steps: Reduction with hydrogen at a temperature of about 50000, optionally followed by sulfurization of a catalyst as defined in any one of Claims l to 12 and Contacting the charge of hydrocarbons and hydrogen with the catalyst so prepared ur,6er conventional hydroreforming condiuions.

   0

   too* DATED this 30th day o f November, 1978. 000

   00 COMPAGNIE FRANCAISE DE RAFFINAGE

   C

   S.. EDWD. WATERS SONS PATENT P"TORNEYS 5 50 QUEEN STREET MELBOURNE VICTORIA 6* 0 AUSTRALIA.

   0 0 0 00

   00

   WMcM/EH

   23

   V/'